Color forming compounds containing sulphonamide groups



Patented Jan. 27, 1942 COLOR FORMING COMPOUNDS CONTAINING SULPHONAMIDE GROUPS Paul W. Vittum, Willard D. Peterson, and Henry D. Porter, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a. corporation of New Jersey No Drawing. Application April 5, 1939, Serial No. 266,152. In Great Britain March 31, 1939 7 Claims;

This invention relates to photographic color forming compounds and particularly ,to color forming coupler compounds containing sulphonamide groups.

The use of color forming compounds which react with the development product of primary aromatic amino developing agents to form color images on photographic development, is well known and has been the subject of numerous prior patents. The dyes formed in this way are insoluble in water and in the ordinary photographic developing and fixing baths although the silver images formed simultaneously with them during the photographic development may be removed from the photographic layer to leave pure dye images in the layer. The coupler compounds used in this way may be added to the developing solution or in certain cases may be incorporated in the photographic layer prior to exposure. When the coupler compounds'are incorporated in the developing solution, it is desirable that they be sufliciently soluble in the developing solution so that amounts may be used which produce suiliciently high dye densities in the resulting photographic image. In many cases the coupler compounds are not sufliciently soluble in thedeveloper and steps must be taken'to increase their solubility.

In Schinzel application Serial No. 263,945, filed March 24, 1939, a continuation-in-part of Serial No. 151,811, filed July 3, 1937, phenolic and naphtholic coupler compounds are described which contain sulphonamide groups in which the sulphur of the sulphonamide is attached to the phenol or naphthol. These "compounds are highly soluble in the developing solutions and produce dyes which are transparent and are not cloudy or opaque as is the case with many dyes produced in this way. These dyes are, however, subject to decomposition by the action of heat and light and it is, therefore, desirableto produce dyes having the solubility and light transmission characteristics of the dyes described in the Schinzel application but which are more stable to heat and light. v

It is, therefore, an object of the present invention to provide novel photographic coupler compounds having desirable properties with respect to heat and light stability. A further object is to provide photographic couplers which are highly soluble in developing solutions. A stillfurther object isto provide photographic couplers which produce transparent yellow dyes on photographic development. A still further objectv is to provide coupler compounds which produce.

dyes of desirable light transmission character-- istics for multi-color photography. Other objects will appear from the following description of our invention..

These objects are accomplished by the use of certain coupler compounds containing sulphonamide groups.

The color-forming compounds which we have found to be useful are compounds of the general structure R COCHzCONH-R'Su where R represents an alkyl, aryl, or furoyl radical, R represents an arylene radical, and Su represents a sulphonamide group, such as SO2NH-- or -NHSO2.

Couplers forming yellow dyes v BOzNHs p-gw-Benzoylacetamino)-benzenc-sulphonamide Nn-oo-onroo-cm.

OINHCH! p-(w-Benzoylacetamlno)-benzene-sulphon-N-methylamide S O z-NH -CoHi p-(u-Benmylacetamino)-benzone sulphonanilide NH- S 0 3 'C H5 4-benzenesulphonamino-o-benzoylacetanilide NHC O-CHz-C OCOH5 i-(p-toluonesulphonamino) -w-benzoylacetanilide 4 5, NH-S 0200111125 e (p-leurylbenzezxesulph onamino) -w-b enzoylscellanilide NE-S Oz NH-C 0 -01126 0 CGHL Q-s OGNH-C o omc 0 can 1,4-61-(p-(benzcyloceteminc)-henzenesulpl1onamino)-benzene N N Benzoylecetyl-N(Zhenzothiazolyh-sulphanilamide IJ-Acetoecetamiuobcnzene-eulphon-fi-naphthalide p=Furoylacetamino-beuzenesulphomN-cyolohcxylamids I S OzNH:

p=(4-ethoxybcnzoylacetamlno)-benzene sulphonamide 75 Terephtheleyl-bls-{(p-N-omylsulplmnamido)-acetanllide] p-(Qulnollnwsulphonamlno)-ebenzoylacetanlllde NE-CO-CE:-OO-CH;

I p-Acetoacetam!no-omothylbenzcnesulphomN-anllidc N, Noi-(p ncnzoyI-acctamluophenol)-naphthdene- 1, odisulphoncmlde NH-SO p-(Benzonesulphonamino)-bonzoylecetonc The coupler compounds having the general formulae: R-=COCIhCONH -R'-Su contain a methylene group which is reactive with the oxldotlon product of primary aromatic amino photographic developers to produce yellow dyes.

The following example, which is illustrative only, indicates developing solution containing,

one of the coupler compounds used according to our invention.

Example 1 A. pAminodlmetl1ylanlllnesulpha-te "aroma- 2.5 Sodium sulphite (anhydrous) do 2 Sodium carbonate (enhyclrousludouu 2O Potasslunibromide"; "010"." 1 Wat-er to cc- 1G0) E. pw-Bemoymccta'mino)-benzenesul phona-mide gra-m-= 2 Sodium hydroxide-40% solutiouflecu 10 B is added to A In the foregoing example, we have described adding the coupler. compound to the developing solution itself. Although itwill usually be em ployed in this way, the coupler compound may also be incorporated in the photographic layer prlor to exposure and the colored image formed by development of the layer in the primary aromatic amino developing solution. Special dis,

perslng agents may be used for incorporating the coupler compound in the emulsion and in certain cases the coupler may be absorbed or adsorbed to the sensitive salt or may be combined with the sensitive salt as a chemical combination. In the case of a multi-layer photographic film in which color forming compounds may be .incorporated in one or more of the layers, it may be necessary to take special precautions to prevent wandering of the coupler compound from the sensitive layer in which it is incorporated. Certainof the coupler compounds described in the present application are in themselves non-diffusing and may be incorporated in the photographic layer without the use of additional agents .to'

prevent difl'usion.

an example of this typecoupler.

The sulphonamide group, because of its solubilizing effect, has a very important advantage in connection with non-diffusing couplers in that it makes dispersion or the couplers very much easier. Thus it is possible to have a coupler of high molecular weight which is completely nondiffusing and yet which is simply and easily dispersed due to the salt-forming properties of the SO'.-NH- group.

The aromatic amino developing agents usedwith the coupler compounds of our invention include the mono, di and triaminoaryl compounds 3 The examples and compounds set forth in the present specification are illustrative only and it is to be understood that our invention is to be taken as limited only by the scope of the appended claims. Where we describe organic groups such as aryl, arylene, alkyl, and sulphonamide in the specification and claims, we intend to include the substituted, as well as unsubsti- The compound 4-(p-lauryl Y benzenesulphonamino)-w-benzoyl acetanilide isand their derivatives rormed by substitution in the amino group as well as in the ring, such as alkylphenylenediamines and alkyltoluylenediamines. These compounds are usually used in the salt form; such as theihydrochloride or the sulphate, which are more stable than theamines themselves. Suitable compounds are diethyl-pphenylenediamine hydrochloride, monomethyl-phenylenediaminehydrochloride, dimethyl-pphenylenediaminehydrochloride, and dimethyl-pphenylenediaminesulphate. The p-aminophenols and their substitution products may also be used where the amino group is unsubstituted. All of these compounds have an unsubstituted amino group which enables the oxidation products of the developer to-couple with the color forming compounds to form a dye image.

Our development process may be employed for the production of colored photographic images in layers of gelatin or other carrier, such as collodion, organic esters of cellulose, or synthetic resins. The carrier may be supported by a transparent medium such as glass, a cellulose ester or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the support or as superposed layers on one or both sides of the support. The superposed layers may be differentially sensitized and the dyes formedwhere R is an aryl radical, R is an arylene rad- I tuted, groups, exceptwhere certain groups are specifically excluded.

What we claim is: x

1. A color forming photographic developer comprising an aromatic amino developing agent and a coupler compound having the tormulaz.

. R-.COCH2CONH-R' -Su where R is selected from the group consisting of alkyl, aryl and iuroyl radicals, R is an arylene radical and Su is a sulphonamide group.

2. A color forming photographic developer comprising an aromatic amino developing agent and a coupler compound having the formula where R is an aryl radical, R is an arylene rad- 5 ical, and Su is a sulphonamide group. I

3. A color' forming. photographic developer comprising a primary aromatic amino developing agent and a coupler compound having the formula: R-COCHqCONH-R'-Su where R is an aryl radical, R is a phenylene radical and Su is a sulphonamide group.

4-. A color Iormin'g photographic developer comprising a primary aromatic amino develop-' ing agent and a coupler compound having the formula ncocn,o onu-O-nnsonv where R and R are aryl radicals.

5. A color forming photographic develope comprising a primary aromatic amino developing agent and a coupler compound having the formula:

11-0 0 ciao ounG-somnnn where R and R are aryl radicals.

6. The method of producing a colored photographic image in a gelatino-silver halide emulsion layer, which comprises exposing the layer and developing it with a primary aromatic amino developing agent in the presence 0! a coupler having the formula compound R-COCH:CON H R'Su ical, and Su is a sulphonamide group.

'I. A photographic emulsion for forming colored images comprising a carrier containing a sensitive silver halide and a coupler compound having the formula R-COCH2CONHR'8u where R is an aryl radical, R is an arylene radical, and Su is a sulphonamide group.

PAUL- W. VITTUM. WILLARD D. PETERSON. HENRY D. PORTER. 

